Synergistic pesticidal composition of pyrazole and N-phenyl-pyrazole

ABSTRACT

The present invention provides an insecticidal composition comprising, as active ingredients, (a) at least one pyrethroid compound and (b) an N-aryldiazole compound such as 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl-4-trifluoromethylsulfinylpyrazole, and an insecticidal method which comprises applying the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application No. 08/700,520, filed Dec.11, 1996 now U.S. Pat. No. 5,747,519, which is the U.S. National Phaseof International Application No. PCT/EP95/00601, filed Feb. 20, 1995.

The present invention relates to a termite control composition for soiltreatment containing a 3-cyano-1-(substituted phenyl)-pyrazolederivative and a pyrethroid compound as effective ingredients.

The pyrazoles derivatives as effective ingredients of the termitecontrol composition of the present invention are known compoundsdescribed in European patent application 295117 as well as ininternational patent applications WO 9316089 and 94/21606, whichdisclose that the compounds have a pesticidal effect on arthropods,vegetable nematodes, protozoan pests, and other pests. Many otherpesticidal compounds can be used in combination with N-phenyl pyrazolederivatives. Pyrethroid compounds such as cyfluthrin, cypermethrin,deltametdrin, fenpropathrin, fenvalerate, and permethrin are recitedamong many possibilities without any reference to any specific effect inany conditions.

A first object of the instant invention is to provide synergisticcompositions of 3-cyano-1-(substituted phenyl)-pyrazole derivative.

Another object of the instant invention is to provide specificcompositions which have an improved activity against pests, especiallyagainst insects.

Another object of the instant invention is to provide specificcompositions which have an improved activity against termites.

There are mainly two types of termite control methods: namely, woodapplication by applying a control agent to wood, and soil treatment byspraying a control agent on the soil and/or under the floor. Forexisting houses, since the application of the agent to wood is ratherdifficult, soil treatment is generally used. In many cases, however,termites pass through the treated layer and eat the wood, and,therefore, it is desired to develop a termite control agent which hasboth the termite control effect and the ability to prevent termites frompassing through the pesticidally treated layer.

A further object of the instant invention is to provide a novel termitecontrol composition (preferably for soil treatment) which has a strongtermite control effect as well as the ability to prevent termites frompassing through the pesticidally treated layer.

It has been found that these goals may be reached by mean of thecompositions of the instant invention.

The compositions of the present invention comprise, as effectiveingredients, a pyrethroid compound and a compound of formula (I) 1- 4-R¹2,6-(R²)p phenyl!3-cyano 4- R⁴ -S(O)_(n) !5-R⁵ pyrazole (I)

wherein:

R¹ is halogen, lower haloalkyl, lower haloalkoxy or SF₅ (lower being aninteger from 1 to 4, preferably one),

R² is halogen, the various R² being identical or different,

R⁴ is halogen, lower alkyl or haloalkyl,

R⁵ is halogen, lower alkyl or amino,

n is 0 or 1 or 2; p is 1 or 2 or 3 or 4, preferably 2.

Halo before the name of a radical means that this radical may besubstituted by one or more halogen atoms.

A preferred compound of formula (I) is5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)4-trifluoromethylsulphinylpyrazole (compound A).

The compositions of the invention comprise a synergistically amount ofactive ingredients.

Pyrethroid compounds which can be used in the present invention includeall kind of pyrethroids, especially pyrethroids other than cyfluthrin,cypermethrin, deltamethrin, fenpropathrin, fenvalerate, and permethrin.Advantageously, pyrethroids which can be used in the invention arecompounds selected from a group consisting of the following pyrethroidcompounds, even tough not limited to these pyrethroid compounds:

1. Allethrin dl-3-allyl-2-methyl4-oxo-2-cyclopentenyl-dl- cis,trans-chrysanthemate!

2. Ethofenprox 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether!

3. Cycloprothrin (RS)-a-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-(4-ethoxyphenyl)-cyclopropane carboxylate!

4. Cyhalothrin (RS)-a-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS)3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl- cyclopropanecarboxylate!

5. Cyfluthrin (RS)-a-cyano-4-fluoro-3-phenoxybenzyl (1RS, 3RS)-(IRS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropane carboxylate!

6. Cypermethrin (RS)-a-cyano-3-phenoxybenzyl (1RS,3RS)-(1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropanecarboxylate!

7. Pyrethrin

8. Tralomethrin (S)-a-yano-3-phenoxybenzyl (1R,3S)-2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)-cyclopropane carboxylate!

9. Fenvalerate (RS)-a-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methylbutanoate!

10. Fenpropathrin (RS)-a-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane carboxylate!

11. Flucydirinate(RS)-a-cyano-3-phenoxybenzyl-(S)-2-(4-difluoromethoxyphenyl)-3-methylbutylate!

12. Pernethrin 3-phenoxybenzyl (1RS, 3RS)-(1RS,3RS)-(2,2-dichlorovinyl)-2,2-dimethyl cyclopropane carboxylate!

13. Bifenthrin ² -methylbiphenyl-3-yl-methyl (Z)-(1RS, 3RS)-3-(2-ischloro-3,3, 3-trifluoroprop-1-enyl)-2,2-dimethyl cyclopropanecarboxylate!

14. Silafluofen ⁴ -ethoxyphenyl- 3-(3-phenoxy4- fluorophenyl)propyl!(dimethyl) silane!

15. Lesmethrin 5-benzyl-3-furylmethyl dl-cis, trans- chrysanthemate!

16. Tefluthrin 2,3,5, 6-tetrafluoro4-methylbenzyl-(IRS)-cis-3-(Z-2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-diethyl cyclopropanecarboxylate!

17. Acrinathrin (S)-a-cyano-3-phenoxybenzyl (Z)-(1R, 3S)-2,2-dimethyl-3-2-(2,2,2-trifluoro-1-trifluoromethyl ethoxycarbonyl) vinyl!cyclopropanecarboxylate!

18. Prarethrin (RS)-2-methyl4-oxo-3-prop-2-enylcyclopent- 2-enyl(1RS)-cis, trans-2,2dimethyl-3-(2-methyl prop-1-enyl) cyclopropanecarboxylate!

19. Cismethrin 5-benzyl-3-furylmethyl (1R)-trans-2,2-dimethyl-3-(2-methyl prop-1-enyl) cyclopropane carboxylate!

20. d-Phenothrin 3-phenoxybenzyl (1RS)-cis, trans-2,2-dimethyl-3-(2-methyl prop-1-enyl) cyclopropane catboxylate!

21. Deltamethrin (S)-a-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylate!

22. Tetramethrin cyclohex-1-ene-1,2-dicarboximide methyl (1RS, 3RS, 1RS,3SR)-2,2dimethyl-3-(2-methyl prop-1-enyl) cyclopropane carboxylate!.

The synergistic compositions of the invention are compositions whereinthe ratio by weight of the pyrethroid compound to the compound offormula (I) is between 0.1 and 10, preferably between 0.5 and 5.

The synergistic compositions of the invention are compositions, whichare most useful for termite control, preferably with soil treatment.Thus, the invention is also directed to a method of control of pests,especially of termites which comprises applying an effective amount ofthe compositions according to the invention, as herein described.

The liquid compositions of the invention generally comprise 0.001 to 50%(all percentages are by weight in the instant specification, unlessspecifically indicated otherwise) of compound of formula (1), preferablyfrom 0.005% to 10. The concentrated composition which are those used forstorage and commercial purpose comprise generally from 1 to 20% of thiscompound of formula (I).

When the compositions for soil treatment of the present invention areused for termite control, especially for soil treatment and/or fortreating under-floor soil, the quantity of the effective ingredient maybe within a range between 0.01 g and 7 g, preferably between 0.1 g and 5g per square meter. For wood treatment, such as timber or all kind ofwood, the method of control of pest, especially of termites, accordingto the invention is impregnating the wood by mean of a composition asherein before defined.

The application of the compositions of the invention to animals isgenerally made at 0.1 to 100 mg, preferably at 2 to 20 mg per kilogramof body weight of the animal.

The termite control composition of the present invention has a highlysignificant termite control effect on houses damaging termites, forexample Coptotermes formosanusus, (Shiraki), Reticulitermes speratus(Kolbe), Odontotermes formosanus(Shiraki), and Cryptotermes domesticus(Haviland), as well as the ability to prevent termites from passingthrough pesticidally treated materials. The composition may be appliedto or adsorbed in building materials, furniture, leather, fabrics, vinylcoated articles, electric wires, or cables.

For the efficient use of the termite control composition for material orsoil treatment of the present invention, the composition may bedissolved, suspended, mixed, adsorbed, or adhered on an appropriatesolid and/or liquid vehicles (this word is used as a synonym of"carrier") according to the formulation generally used, together withauxiliary agents if required. This composition may be formulated intoforms suited to the object of use, for example, an oil solution,emulsion, water solution, powder, granules, wettable powder, aerosol,smoking agent, or flowable agent.

Solid vehicles used in the present invention include, for example, clayssuch as kaolin, bentonite, and acid clay; talc materials such as talcand pyrophylite; siliceous materials such as diatomaceous earth, silicasand, mica, synthetic silicates, and high dispersion syntheticsilicates; and inorganic mineral powders such as pumice and sand. Liquidvehicles include, for example, alcohols such as methanol, ethanol, andethylene glycol; ketones such as acetone, methylethyl ketone, andcyclohexanone; ethers such as ethyl ether, dioxane, tetrahydrofuran, andcellosolve; aliphatic hydrocarbons such as kerosene; aromatichydrocarbons such as benzene, toluene, xylene, solvent naphtha,cyclohexane, and methyl naphthalene; and halogenated hydrocarbons suchas chloroform, carbon tetrachloride, and chlorobenzene. These solid orliquid vehicles may be used alone or in combination.

Auxiliary agents used in the present invention include propellants,surface-active agents, fixing agents, dispersing agents, thickeningagents, and bonding agents. Propellants include, for example, liquefiedpetroleum gas, dimethyl ether, and fluorocarbons. Surface-active agentsinclude, for example, polyoxyethylene alkylaryl ether, polyoxyethylenesorbitane monolaurate, alkylallyl sorbitane monolaurate, alkylbenzenesulfonate, alkylnaphthalene sulfonate, lignin sulfonate, and sulfuricacid ester salts of higher alcohols. These surface-active agents may beused alone or in combination.

Fixing agents, dispersing agents, thickening agents, and bonding agentsinclude, for example, casein, gelatine, starch, carboxymethyl cellulose,alginic acid, agar, polyvinyl alcohol, polyethylene glycol, polysodiumacrylate, gum arabic, and xanthane gum, which may be used if required.

The termite control composition for soil treatment of the presentinvention may contain co-operating agents such as sinepyrin 500,piperonyl butoxide, and S421.

The termite control composition of the present invention may be used notonly for treating the surface or the interior of surrounding soil orunder-floor soil for protecting wood such as trees, fences, and railroadties, or buildings such as houses, warehouses, and industrial plants,but also in timber products such as plywood and furniture, wood productssuch as particle boards and half boards, and vinyl products such ascoated wires and sheets.

The present invention also includes the aspects for preventive uses inplaces where the breeding of termites is expected as well as the aboveaspects.

Emulsifying agents which may be used are one or more of those selectedfrom non-ionic or anionic emulsifying agents. Examples of non-ionicemulsifying agents which may be mentioned includepolyoxyethylenealkylphenylether, polyoxyethylenealkylether,polyethyleneglycol fatty ester, sorbitan fatty ester, polyoxyethylenesorbitan fatty ester, polyoxyethylenesorbitol fatty ester,polyoxyethylenepolyoxy-propyleneaLkylether. Examples of anionicemulsifying agents which may be mentioned include alkyl sulphates,polyxyethylenealkylether sulphates, sulfosuccinates, taurinederivatives, sarcosine derivatives, phosphoric esters,alkylbenzenesulfonates and the like. A mixture consisting ofpolyoxyethylenestyrylphenylether and calcium alkylbenzenesulfonate ispreferred. These emulsifying agents may be used in an amount of 5 to 20weight parts per 100 weight parts of the composition of the presentinvention.

Compositions of the present invention may be prepared by any ofconventional procedures suitable for emulsifiable concentrates.

The present invention is illustrated by the following examples,comparative examples and experimental examples, but is not limited tothe details thereof.

EXAMPLES

Typical embodiments and test examples of the present invention will beshown below, but the present invention is not limited to theseembodiments.

In the description of these embodiments, the term "part(s)" meanspart(s) by weight. The test method of embodiments was in accordance withJapan Wood Preservation Association Standards No. 13, 1987, "Standardsfor Testing Methods of Termite Controlling Effects and Performance ofTermite Controlling Agents for Soil Treatment

    ______________________________________    Embodiment 1    ______________________________________    Compound A              8.00 parts    Bifenthrin              2.00 parts    Propylene glycol        5.00 parts    Anionic surface-active agent                            1.00 part    Non-ionic surface-active agent                            5.00 parts    Xanthane gum            0.25 parts    Silicone defoaming agent                            0.50 parts    Water                  78.25 parts    ______________________________________

The above materials are uniformly mixed and suspended to form a flowableagent.

    ______________________________________    Embodiment 2    ______________________________________    Compound A              1.00 part    Bifenthrin              0.40 parts    Propylene glycol        5.00 parts    Anionic surface active agent                            1.00 part    Non-ionic surface-active agent                            5.00 parts    Xanthane gum            0.40 parts    Silicone defoaming agent                            0.50 parts    Water                  86.70 parts    ______________________________________

The above materials are uniformly mixed and suspended to form a flowableagent.

    ______________________________________    Embodiment 3    ______________________________________    Compound A              4.00 parts    Permethrin             20.00 parts    Anionic surface-active agent                           10.00 parts    N-methyl-2-pyrrolidone 10.00 parts    Aromatic solvent       56.00 parts    ______________________________________

The above materials are uniformly dissolved to form an emulsion.

Test example 1

A testing apparatus was used in which two glass cylinders (each about 5cm in diameter and about 12 cm in height) are connected at about 2 cmfrom the bottom with a glass tube about 1.5 cm in diameter and about 10cm in length (graduated at 5-mm intervals for 5 cm at the center). Theone glass cylinder was filled with about 60 g of non- treated soiladjusted to a moisture content of about 25%, and the other glasscylinder was filled with about 0.29 g of filter paper (5.5 mm indiameter). The glass tube was filled, at a thickness of 1 cm, with testsoil prepared by mixing 2.4 g of non- treated sandy soil which hadpassed through a 20-mesh screen and had been dried at 60° C. until aconstant weight had been achieved, with 0.45 g of the solution of thetest composition of a predetermined concentration, and allowing themixture to stand for 3 weeks in a room without weather resistancetreatment. The glass tube was connected to the glass cylinders.

In the glass cylinder filled with non treated soil, placed were 200workers and 20 soldiers of Cototermes formosanus Shiraki, and thetesting apparatus was kept at a constant temperature chamber controlledat a temperature of 28° C., and a relative humidity of 70% or higher.

The bored depth (millimeters =mm), damage by eating, and the termitecontrol effect were determined 14 days after insects were put in place,and the effect was evaluated in accordance with the following criteria:

    ______________________________________    Damage by eating:    +            10% or less compared with non treatment    ++           11-50% or less compared with non treatment    +++          51% or more compared with nontreatment    Termite control effect:    A            100% lethal    B            80-99% lethal    C            50-79% lethal    D            49% lethal or less    ______________________________________

Results are shown in Table 1:

    __________________________________________________________________________                         Bored depth                               Damage by                                     Termite          Test   Con-    (mm) 14                               eating 14                                     control effect          composition                 centration (%)                         DAT   DAT   14 days later    __________________________________________________________________________    Em-   compound A +                 0.01 + 0.01                         3     None  A    bodiments          bifenthrin                 0.01 + 0.005                         2     None  A                 0.005 + 0.01                         3     None  A                 0.005 + 0.005                         7     None  A                 0.0025 + 0.01                         5     None  A                 0.0025 + 0.005                         9     None  A                 0.00125 + 0.01                         7     None  A                 0.00125 + 0.005                         9     None  A    Em-   Compound A +                 0.02 + 0.05                         2     None  A    bodiments          fenvalerate                 0.005 + 0.05                         6     None  A                 0.02 + 0.01                         1     None  A                 0.005 + 0.01                         3     None  A          Compound A +                 0.02 + 0.025                         0     None  A          cypermethrin                 0.005 + 0.025                         0     None  A                 0.02 + 0.005                         2     None  A                 0.005 + 0.005                         3     None  A          Compound A +                 0.02 + 0.1                         0     None  A          permethrin                 0.05 + 0.1                         6     None  A                 0.02 + 0.02                         8     None  A          Compound A +                 0.02 + 0.01                         6     None  A          tralomethrin                 0.005 + 0.01                         4     None  A                 0.02 + 0.002                         2     None  A                 0.005 + 0.002                         8     None  A          Compound A +                 0.02 + 0.05                         8     None  A          fluvalinate          Compound A +                 0.02 + 0.025                         6     None  A          cyfluthrin                 0.005 + 0.025                         6     None  A                 0.02 + 0.005                         6     None  A          Compound A +                 0.02 + 0.1                         2     None  A          cthofenprox                 0.005 + 0.1                         8     None  A                 0.02 + 0.02                         4     None  A                 0.005 + 0.02                         7     None  A          Compound A +                 0.02 + 0.05                         6     None  A          silafluofen                 0.005 + 0.05                         5     None  A                 0.02 + 0.01                         7     None  A    __________________________________________________________________________                         Bored depth                               Damage by                                     Termite          Test   Con-    (mm) 14                               eating                                     control effect          composition                 centration (%)                         days later                               14 days later                                     14 days later    __________________________________________________________________________    Comparative          Compound A                 0.02    >10   +     A    examples     0.01    >10   +     A                 0.005   >10   ++    A          Bifenthrin                 0.01    >10   +++   D                 0.005   >10   +     D          Fenvalerate                 0.05    >10   +     A                 0.01    >10   +++   D          Cyperme-thrin                 0.025   >10   None  D                 0.005   >10   +++   D          Permethrin                 0.1     >10   None  D                 0.02    >10   +++   D          Tralomethrin                 0.01    >10   +++   D                 0.002   >10   +++   D          Fluvalinate                 0.05    >10   +++   D          Cyfluthrin                 0.025   >10   None  D                 0.005   >10   +++   D          Ethofenprox                 0.1     >10   None  D                 0.02    >10   +++   D          Silafluofen                 0.05    >10   +     A                 0.01    >10   +++   D          Non-treatment  >10   +++   D    __________________________________________________________________________

What is claimed is:
 1. A termiticidal combination comprising (a)permethrin and (b) 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole,in a combined synergistic termiticidally effective amount, the ratio byweight of (a) to (b) being between 1 and
 20. 2. A combination as claimedin claim 1, wherein the ratio by weight of (a) to (b) is between 1 and5.
 3. A termiticidal composition comprising:(a) permethrin and (b)5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole,in a combined synergistic termiticidally effective amount, the ratio byweight of (a) to (b) being between 1 and 20, and (c) an acceptablecarrier therefor.
 4. A composition as claimed in claim 3, wherein theratio by weight of (a) to (b) is between 1 and
 5. 5. A composition asclaimed in claim 3, being in liquid form and comprising from 0.001% to50% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.6. A composition as claimed in claim 4, being in liquid form andcomprising from 0.001% to 50% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.7. A composition as claimed in claim 4, comprising from 0.005% to 10% byweight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.8. A composition as claimed in claim 6, comprising from 0.005% to 10% byweight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.9. A composition as claimed in claim 3, being in the form of aconcentrate and comprising from 1 % to 20% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.10. A composition as claimed in claim 4, being in the form of aconcentrate and comprising from 1% to 20% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.11. A method for controlling termites and for preventing them frompassing through a layer of soil or other material, said methodcomprising treating said layer with a termiticidally effective amount ofa termiticidal composition comprising (a) permethrin and (b)5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole,in a combined synergistic termiticidally effective amount, the ratio byweight of (a) to (b) being between 1 and 20; and (c) an acceptablecarrier therefor.
 12. A method as claimed in claim 11, wherein the ratioby weight of (a) to (b) is between 1 and
 5. 13. A method as claimed inclaim 11, wherein said composition is in liquid form and comprises from0.001% to 50% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.14. A method as claimed in claim 12, wherein said composition is inliquid form and comprises from 0.001 % to 50% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.15. A method as claimed in claim 13, wherein said composition comprisesfrom 0.005% to 10% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.16. A method as claimed in claim 14, wherein said composition comprisesfrom 0.005% to 10% by weight of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole.17. A method as claimed in claim 11, wherein a layer of soil is treatedand wherein an amount between 0.01 g/m² and 7 g/m² of active ingredients(a) and (b) is applied.
 18. A method as claimed in claim 12, wherein alayer of soil is treated and wherein an amount between 0.01 g/m² and 7g/m² of active ingredients (a) and (b) is applied.
 19. A method asclaimed in claim 17, wherein the amount of active ingredients (a) and(b) applied is between 0.1 g/m and 5 g/m².
 20. A method as claimed inclaim 18, wherein the amount of active ingredients (a) and (b) appliedis between 0.1 g/m² and 5 g/m².